WO2018066528A1 - Bouillie, et procédé de fabrication de matériau de résine composite ainsi que de corps moulé - Google Patents

Bouillie, et procédé de fabrication de matériau de résine composite ainsi que de corps moulé Download PDF

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Publication number
WO2018066528A1
WO2018066528A1 PCT/JP2017/035879 JP2017035879W WO2018066528A1 WO 2018066528 A1 WO2018066528 A1 WO 2018066528A1 JP 2017035879 W JP2017035879 W JP 2017035879W WO 2018066528 A1 WO2018066528 A1 WO 2018066528A1
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Prior art keywords
fibrous carbon
resin material
slurry
composite resin
carbon nanostructure
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PCT/JP2017/035879
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English (en)
Japanese (ja)
Inventor
慶久 武山
上野　真寛
徳之 三田尾
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日本ゼオン株式会社
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Application filed by 日本ゼオン株式会社 filed Critical 日本ゼオン株式会社
Priority to US16/335,804 priority Critical patent/US20190276610A1/en
Priority to JP2018543903A priority patent/JPWO2018066528A1/ja
Priority to CN201780059279.2A priority patent/CN109790347A/zh
Publication of WO2018066528A1 publication Critical patent/WO2018066528A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/11—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids from solid polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B29B7/005—Methods for mixing in batches
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/32—Component parts, details or accessories; Auxiliary operations
    • B29C43/52—Heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine
    • C08F14/26—Tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/041—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B29K2105/162—Nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/16—Fillers
    • B29K2105/165—Hollow fillers, e.g. microballoons or expanded particles
    • B29K2105/167—Nanotubes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2507/00—Use of elements other than metals as filler
    • B29K2507/04—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0003—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular electrical or magnetic properties, e.g. piezoelectric
    • B29K2995/0005—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • B29L2007/002—Panels; Plates; Sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/004—Additives being defined by their length
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Definitions

  • the present invention relates to a slurry, and a method for producing a composite resin material and a molded body, and in particular, a slurry containing fluororesin particles and fibrous carbon nanostructures, and production of a composite resin material using the slurry.
  • the present invention relates to a method and a method for producing a molded body using the composite resin material.
  • Fibrous carbon nanostructures such as carbon nanotubes (hereinafter sometimes referred to as “CNT”) are excellent in electrical conductivity, thermal conductivity, sliding characteristics, mechanical characteristics, etc., and therefore are considered to be applied to a wide range of applications. ing. Therefore, in recent years, taking advantage of the excellent properties of fibrous carbon nanostructures, by combining resin materials and fibrous carbon nanostructures, resin properties such as processability and strength, and fibrous properties such as conductivity, etc. Development of a technique for providing a composite resin material having the characteristics of carbon nanostructures is in progress.
  • Patent Document 1 and Patent Document 2 propose a composite resin material in which fibrous carbon nanostructures are dispersed and held on the surface of a particulate resin material (hereinafter sometimes referred to as “resin particles”). ing.
  • the composite resin material described in Patent Document 1 is a process of mixing fibrous carbon nanostructures using ultrasonic waves on the surface of resin particles swollen and softened in subcritical or supercritical carbon dioxide. It is manufactured by the manufacturing method containing. According to such a manufacturing method, the fibrous carbon nanostructure is dispersed over substantially the entire surface of the resin particles by the action of ultrasonic waves, and is further embedded firmly from the surface of the resin particles toward the inside.
  • the composite resin material described in Patent Document 2 is swelled and softened by gently stirring a mixed liquid of fibrous carbon nanostructures and resin particles in a subcritical or supercritical carbon dioxide atmosphere. It is manufactured by a manufacturing method including a step of adsorbing fibrous carbon nanostructures on the surface of resin particles. According to this production method, composite resin particles can be produced without dividing the fibrous carbon nanostructure.
  • the composite resin material containing fibrous carbon nanostructure has electroconductivity, it is used for manufacture of the molded object which has antistatic ability, for example.
  • the molded article having antistatic ability has excellent mechanical strength, uniform conductivity, and sufficiently low surface resistivity (for example, less than 10 8 ⁇ / sq). Is required.
  • the molded body formed using the conventional composite resin material may have uneven conductivity.
  • an object of the present invention is to provide a molded article having excellent mechanical strength and sufficiently low surface resistivity, and a composite resin material capable of forming the molded article.
  • the present inventor has intensively studied to achieve the above object.
  • the inventor uses a composite resin material obtained by removing the dispersion medium from the slurry containing the fluororesin particles, the fibrous carbon nanostructure, and the dispersion medium and having a predetermined property.
  • the present inventors have found that a molded article having excellent mechanical strength and sufficiently low surface resistivity and excellent antistatic performance can be obtained.
  • the present invention aims to advantageously solve the above problems, and the slurry of the present invention is a slurry containing fluororesin particles, fibrous carbon nanostructures, and a dispersion medium. , Containing 100 parts by mass of the fibrous carbon nanostructure per 100 parts by mass of the fluororesin particles, and putting it in a slide glass with a groove having a depth of 0.5 mm.
  • the fibrous carbon nanostructure preferably has an average diameter of 1 nm to 60 nm and an average length of 10 ⁇ m or more. This is because if the average diameter and average length of the fibrous carbon nanostructure are within the above ranges, the surface resistivity of the molded body obtained using the slurry can be further reduced.
  • the “average diameter of the fibrous carbon nanostructure” means, for example, the diameter (outer diameter) of 20 fibrous carbon nanostructures measured on a transmission electron microscope (TEM) image. It can be obtained by calculating the number average value.
  • “average length of fibrous carbon nanostructures” is, for example, by measuring the length of 20 fibrous carbon nanostructures on a scanning electron microscope (SEM) image and calculating the number average value. You can ask for it.
  • the fibrous carbon nanostructure has a shape in which a t-plot obtained from an adsorption isotherm is convex upward. This is because the use of a fibrous carbon nanostructure whose t-plot has an upwardly convex shape can further reduce the surface resistivity of the molded body obtained using the slurry.
  • the dispersion medium preferably has a Hansen solubility parameter dispersion term dD of 16 or more and 22 or less and a hydrogen bond term dH of 0 or more and 6 or less. This is because the surface resistivity of the molded body can be further reduced by using a slurry using the dispersion medium having the above properties.
  • the dispersion medium is preferably at least one selected from the group consisting of cyclohexane, xylene, methyl ethyl ketone and toluene. This is because the surface resistivity of the molded article can be further reduced by using a slurry using at least one selected from the group consisting of cyclohexane, xylene, methyl ethyl ketone and toluene as a dispersion medium.
  • this invention aims at solving the said subject advantageously, and the manufacturing method of the composite resin material of this invention removes the said dispersion medium from any of the said slurry, and uses a composite resin material. A step of forming. By removing the dispersion medium from the slurry, it is possible to obtain a composite resin material that can form a molded article having excellent mechanical strength and sufficiently low surface resistivity.
  • this invention aims at solving the said subject advantageously, and the manufacturing method of the molded object of this invention shape
  • the composite resin material which is excellent in mechanical strength and can form the molded object with sufficiently low surface resistivity can be obtained.
  • a composite resin material that is excellent in mechanical strength and capable of forming a molded article having a sufficiently low surface resistivity can be obtained.
  • a molded article having excellent mechanical strength and sufficiently low surface resistivity can be obtained.
  • the slurry of this invention can be used when manufacturing a composite resin material using the manufacturing method of the composite resin material of this invention.
  • the composite resin material manufactured using the manufacturing method of the composite resin material of this invention can be used when manufacturing a molded object using the manufacturing method of the molded object of this invention.
  • the molded object manufactured using the manufacturing method of the molded object of this invention has low surface resistivity and antistatic ability, it is not specifically limited, For example, trays for integrated circuits, wafer carriers It is useful as a sealing material.
  • the slurry of the present invention contains fluororesin particles, fibrous carbon nanostructures, and a dispersion medium, and optionally further contains an additive such as a dispersant.
  • the slurry of the present invention includes a fibrous carbon nanostructure at a ratio of 0.01 parts by mass or more and 0.5 parts by mass or less per 100 parts by mass of the fluororesin particles, and has a groove with a depth of 0.5 mm.
  • the area ratio S (%) of the aggregates of fibrous carbon nanostructures in the observed range When placed in a slide glass and observing a 3 mm ⁇ 2 mm range in the groove of the slide glass using an optical microscope, the area ratio S (%) of the aggregates of fibrous carbon nanostructures in the observed range, The volume fraction V (volume%) of the fibrous carbon nanostructure in the total solid content (100 volume%) of the slurry satisfies a predetermined relationship.
  • the slurry of the present invention contains fibrous carbon nanostructures at a predetermined ratio, and the area ratio S (%) and the volume fraction V (volume%) satisfy a predetermined relationship, If a composite resin material obtained by removing the dispersion medium from the slurry is used, a molded article having excellent mechanical strength and sufficiently low surface resistivity can be obtained.
  • the fluororesin constituting the fluororesin particles is a polymer containing a fluorine-containing monomer unit.
  • “comprising a monomer unit” means “a repeating unit derived from a monomer is contained in a polymer obtained using the monomer”.
  • fluororesin examples include polytetrafluoroethylene (PTFE), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene hexafluoropyrene copolymer (FEP), and tetrafluoroethylene ethylene copolymer.
  • PTFE polytetrafluoroethylene
  • PFA tetrafluoroethylene perfluoroalkyl vinyl ether copolymer
  • FEP tetrafluoroethylene hexafluoropyrene copolymer
  • tetrafluoroethylene ethylene copolymer examples thereof include a polymer (ETFE), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene ethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF), and polyvinyl fluoride (PVF).
  • PTFE or PFA is preferable and PTFE is more preferable
  • the average particle diameter of the fluororesin particles is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, further preferably 10 ⁇ m or more, preferably 700 ⁇ m or less, and 250 ⁇ m or less. Is more preferable, and it is still more preferable that it is 150 micrometers or less.
  • the average particle diameter of the fluororesin particles is 1 ⁇ m or more, the mechanical strength and conductivity of the molded body can be improved.
  • the productivity of the slurry can be improved by setting the average particle diameter of the fluororesin particles to 700 ⁇ m or less.
  • the “average particle diameter” of the fluororesin particles is obtained by measuring the particle size distribution (volume basis) by laser diffraction method and calculating the particle diameter at which the cumulative volume frequency is 50%. Can do.
  • the fibrous carbon nanostructure is not particularly limited, and a conductive fibrous carbon nanostructure can be used.
  • a conductive fibrous carbon nanostructure for example, a carbon nanostructure having a cylindrical shape such as a carbon nanotube (CNT), or a carbon nanostructure in which a carbon six-membered ring network is formed in a flat cylindrical shape.
  • a non-cylindrical carbon nanostructure such as a body can be used. These may be used individually by 1 type and may use 2 or more types together.
  • fibrous carbon nanostructure containing CNT it is more preferable to use as the fibrous carbon nanostructure. If fibrous carbon nanostructures containing CNTs are used, even if the amount is small, the composite resin material and the molded body can be efficiently provided with conductivity, and the surface resistivity of the molded body can be reduced. It is.
  • the fibrous carbon nanostructure containing CNT may be composed of only CNT, or may be a mixture of CNT and fibrous carbon nanostructure other than CNT.
  • the CNT in the fibrous carbon nanostructure is not particularly limited, and single-walled carbon nanotubes and / or multi-walled carbon nanotubes can be used. Preferably, it is a single-walled carbon nanotube. This is because the smaller the number of layers of carbon nanotubes, the better the conductivity of the composite resin material and the molded body and the lower the surface resistivity of the molded body even if the blending amount is small.
  • the average diameter of the fibrous carbon nanostructure is preferably 1 nm or more, preferably 60 nm or less, more preferably 30 nm or less, and still more preferably 10 nm or less. If the average diameter of the fibrous carbon nanostructure is 1 nm or more, conductivity can be stably imparted to the composite resin material and the molded body. Moreover, if the average diameter of the fibrous carbon nanostructure is 60 nm or less, the composite resin material and the molded body can be efficiently provided with conductivity even with a small blending amount, and the mechanical strength of the molded body. Can be improved. Therefore, when the average diameter of the fibrous carbon nanostructure is within the above range, the surface resistivity can be sufficiently lowered while sufficiently securing the mechanical strength of the molded body.
  • the fibrous carbon nanostructure the ratio (3 ⁇ / Av) of the value (3 ⁇ ) obtained by multiplying the standard deviation of diameter ( ⁇ : sample standard deviation) by 3 with respect to the average diameter (Av) is more than 0.20. It is preferable to use a fibrous carbon nanostructure of less than 0.60, more preferably to use a fibrous carbon nanostructure with 3 ⁇ / Av exceeding 0.25, and a fibrous shape with 3 ⁇ / Av exceeding 0.40. More preferably, carbon nanostructures are used. If a fibrous carbon nanostructure having 3 ⁇ / Av of more than 0.20 and less than 0.60 is used, the performance of the composite resin material and the molded body to be produced can be further improved.
  • the average diameter (Av) and standard deviation ( ⁇ ) of the fibrous carbon nanostructure may be adjusted by changing the production method and production conditions of the fibrous carbon nanostructure, or may be obtained by different production methods. You may adjust by combining multiple types of the obtained fibrous carbon nanostructure.
  • the fibrous carbon nanostructure when the diameter measured as described above is plotted on the horizontal axis and the frequency is plotted on the vertical axis, and it is approximated by Gaussian, a normal distribution is usually used. Is done.
  • the fibrous carbon nanostructure has an average length of preferably 10 ⁇ m or more, more preferably 50 ⁇ m or more, further preferably 80 ⁇ m or more, preferably 600 ⁇ m or less, and 500 ⁇ m. Or less, more preferably 400 ⁇ m or less. If average length is more than the said lower limit, a conductive path can be formed in a composite resin material and a molded object with few compounding quantities. And if average length is below the said upper limit, the electroconductivity of a composite resin material and a molded object can be stabilized. Therefore, when the average length of the fibrous carbon nanostructure is within the above range, the surface resistivity of the molded body can be sufficiently reduced.
  • the fibrous carbon nanostructure usually has an aspect ratio of more than 10.
  • the aspect ratio of the fibrous carbon nanostructure was determined by measuring the diameter and length of 100 randomly selected fibrous carbon nanostructures using a scanning electron microscope or a transmission electron microscope. It can be obtained by calculating the average value of the ratio to the length (length / diameter).
  • the fibrous carbon nanostructure has a BET specific surface area of preferably 200 m 2 / g or more, more preferably 400 m 2 / g or more, and further preferably 600 m 2 / g or more. It is preferably 2000 m 2 / g or less, more preferably 1800 m 2 / g or less, and further preferably 1600 m 2 / g or less.
  • the BET specific surface area of the fibrous carbon nanostructure is 200 m 2 / g or more, the conductivity of the composite resin material and the molded body can be sufficiently increased with a small blending amount, and the surface resistivity of the molded body can be sufficiently reduced. And the mechanical strength of the molded body can be improved.
  • the BET specific surface area of a fibrous carbon nanostructure is 2000 m ⁇ 2 > / g or less, the electroconductivity of a composite resin material and a molded object can be stabilized.
  • the “BET specific surface area” refers to a nitrogen adsorption specific surface area measured using the BET method.
  • the fibrous carbon nanostructure has a shape in which the t-plot obtained from the adsorption isotherm is convex upward.
  • the “t-plot” is obtained by converting the relative pressure to the average thickness t (nm) of the nitrogen gas adsorption layer in the adsorption isotherm of the fibrous carbon nanostructure measured by the nitrogen gas adsorption method. Can do. That is, the average thickness t of the nitrogen gas adsorption layer is plotted against the relative pressure P / P0, and the average thickness t of the nitrogen gas adsorption layer corresponding to the relative pressure is obtained from the known standard isotherm to perform the above conversion. To obtain a t-plot of the fibrous carbon nanostructure (t-plot method by de Boer et al.).
  • the growth of the nitrogen gas adsorption layer is classified into the following processes (1) to (3).
  • the slope of the t-plot is changed by the following processes (1) to (3).
  • the t-plot indicating an upwardly convex shape is located on a straight line passing through the origin in a region where the average thickness t of the nitrogen gas adsorption layer is small, whereas when t is large, the plot is The position will be shifted downward.
  • the fibrous carbon nanostructure having such a t-plot shape has a large ratio of the internal specific surface area to the total specific surface area of the fibrous carbon nanostructure, and there are many carbon nanostructures constituting the fibrous carbon nanostructure. It is shown that the opening is formed.
  • the bending point of the t-plot of the fibrous carbon nanostructure is preferably in a range satisfying 0.2 ⁇ t (nm) ⁇ 1.5, and 0.45 ⁇ t (nm) ⁇ 1.5. More preferably, it is in the range of 0.55 ⁇ t (nm) ⁇ 1.0. If the bending point of the t-plot of the fibrous carbon nanostructure is within such a range, the conductivity of the composite resin material and the molded body can be increased with a small amount.
  • the “position of the bending point” is an intersection of the approximate line A in the process (1) described above and the approximate line B in the process (3) described above.
  • the fibrous carbon nanostructure preferably has a ratio (S2 / S1) of the internal specific surface area S2 to the total specific surface area S1 obtained from the t-plot of 0.05 or more and 0.30 or less. If the value of S2 / S1 of the fibrous carbon nanostructure is within such a range, the electrical conductivity of the composite resin material and the molded body can be increased with a small blending amount, and the mechanical strength of the molded body can be improved. Can do.
  • the total specific surface area S1 and the internal specific surface area S2 of the fibrous carbon nanostructure can be obtained from the t-plot.
  • the total specific surface area S1 can be obtained from the slope of the approximate line in the process (1), and the external specific surface area S3 can be obtained from the slope of the approximate line in the process (3). Then, the internal specific surface area S2 can be calculated by subtracting the external specific surface area S3 from the total specific surface area S1.
  • the measurement of the adsorption isotherm of the fibrous carbon nanostructure, the creation of the t-plot, and the calculation of the total specific surface area S1 and the internal specific surface area S2 based on the analysis of the t-plot are, for example, commercially available measuring devices.
  • "BELSORP (registered trademark) -mini” manufactured by Nippon Bell Co., Ltd.).
  • the fibrous carbon nanostructure containing CNT suitable as the fibrous carbon nanostructure preferably has a peak of Radial Breathing Mode (RBM) when evaluated using Raman spectroscopy. Note that there is no RBM in the Raman spectrum of a fibrous carbon nanostructure composed of only three or more multi-walled carbon nanotubes.
  • RBM Radial Breathing Mode
  • the fibrous carbon nanostructure containing CNTs preferably has a ratio of G band peak intensity to D band peak intensity (G / D ratio) in the Raman spectrum of 0.5 or more and 5.0 or less.
  • G / D ratio is 0.5 or more and 5.0 or less, the performance of the composite resin material and the molded body to be manufactured can be further improved.
  • the fibrous carbon nanostructure containing CNT is not particularly limited, and is manufactured using a known CNT synthesis method such as an arc discharge method, a laser ablation method, a chemical vapor deposition method (CVD method), or the like. can do.
  • a fibrous carbon nanostructure containing CNTs for example, supplies a raw material compound and a carrier gas onto a substrate having a catalyst layer for producing carbon nanotubes on the surface, and chemical vapor deposition (CVD) Method), when a CNT is synthesized by a method, the catalyst activity of the catalyst layer is dramatically improved by making a small amount of oxidizing agent (catalyst activating substance) present in the system (super growth method; International Publication No. 2006).
  • the carbon nanotube obtained by the super growth method may be referred to as “SGCNT”.
  • the fibrous carbon nanostructure manufactured by the super growth method may be comprised only from SGCNT, In addition to SGCNT, other carbon nanostructures, such as a non-cylindrical carbon nanostructure, for example May be included.
  • the quantity of the fibrous carbon nanostructure contained in a slurry needs to be 0.01 mass part or more and 0.5 mass part or less per 100 mass parts of fluororesin particle
  • the amount of the fibrous carbon nanostructure is not less than the above lower limit, the electrical conductivity of the composite resin material and the molded body can be increased, the surface resistivity of the molded body can be sufficiently reduced, and the mechanical properties of the molded body Sufficient strength can be secured. Moreover, if the quantity of fibrous carbon nanostructure is below the said upper limit, it can suppress that a nonuniformity arises in the electroconductivity of a molded object. Therefore, when the amount of the fibrous carbon nanostructure is within the above range, the molded body can exhibit sufficient antistatic ability while sufficiently securing the mechanical strength of the molded body.
  • the dispersion medium is not particularly limited, and any dispersion medium capable of dispersing the fluororesin particles and the fibrous carbon nanostructure can be used.
  • a solvent having a Hansen solubility parameter dispersion term dD of 16 or more and 22 or less and a hydrogen bond term dH of 0 or more and 6 or less is preferable as the dispersion medium.
  • the dispersion medium may be at least one selected from the group consisting of cyclohexane, xylene, methyl ethyl ketone, and toluene. It is preferable to use cyclohexane.
  • the additive that can be optionally blended in the slurry is not particularly limited, and may be a known additive such as a dispersant.
  • a dispersing agent the known dispersing agent which can assist dispersion
  • examples of the dispersant include a surfactant, a polysaccharide, a ⁇ -conjugated polymer, and a polymer having an ethylene chain as a main chain. Of these, surfactants are more preferred.
  • the amount of the additive in the slurry is preferably 5 parts by mass or less per 100 parts by mass of the fluororesin particles described above. 0 part by mass (that is, the slurry does not contain an additive).
  • the fibrous carbon nanostructures form a good conductive path in the molded body and increase the conductivity of the molded body. be able to. Moreover, if the ratio (S / V) of the area ratio S to the volume fraction V is not more than the above upper limit value, it is possible to suppress the occurrence of unevenness in the conductivity of the molded body. Therefore, if S / V is within the above range, the molded article can exhibit sufficient antistatic ability. Furthermore, if the ratio (S / V) of the area ratio S to the volume fraction V is not more than the above upper limit value, the mechanical strength of the molded article can be ensured.
  • the area ratio S (%) of the aggregate of the fibrous carbon nanostructure is, for example, the mixing / dispersing conditions of the fluororesin particles, the fibrous carbon nanostructure and the dispersion medium, the type of the dispersion medium, and the fibrous shape Adjustments can be made by changing the type, properties and blending amount of the carbon nanostructure. Specifically, the area ratio S (%) increases if the mixing / dispersing conditions are such that the fibrous carbon nanostructures easily aggregate or the fibrous carbon nanostructures that easily aggregate are used.
  • the slurry described above is not particularly limited, and for example, a dispersion treatment is performed on a mixed solution containing fluororesin particles, fibrous carbon nanostructures, a dispersion medium, and an arbitrary additive.
  • the fluororesin particles, the fibrous carbon nanostructures, and the optional liquid mixture obtained by adding a part of the fluororesin particles, the fibrous carbon nanostructures, and the optional additives to the dispersion medium. It can be prepared by adding the remainder of the additive and subjecting it to a dispersion treatment.
  • the slurry is obtained by mixing and dispersing the fluororesin particles, the fibrous carbon nanostructure, the dispersion medium, and any additive at once, or the fluororesin particles and the fibrous carbon nanostructure.
  • a dispersion medium and an optional additive can be prepared by mixing and dispersing in multiple stages.
  • the slurry is preferably prepared by subjecting a mixed solution containing fluororesin particles, fibrous carbon nanostructures, a dispersion medium, and an optional additive to a dispersion treatment.
  • a propeller mixer for the preparation of the slurry, from the viewpoint of easily obtaining a slurry having the above-described properties, a propeller mixer, a high speed mixer, a dissolver, a homogenizer, an artemizer, a wet jet mill, a colloid mill, a mass collider, and a bead mill
  • a wet dispersion treatment using a wet mixing and dispersing machine such as a sand mill, a ball mill, a sand grinder, an in-line mixer, and a medialess type high-speed stirring and dispersing machine.
  • a wet dispersion process using a medialess wet mixing and dispersing machine more preferably to use a wet dispersion process using a homogenizer or an in-line mixer, and to use a wet dispersion process using a homogenizer.
  • the pressure applied to a liquid mixture in the case of a dispersion process shall be 5 Mpa or less.
  • the manufacturing method of the composite resin material of this invention includes the process of removing a dispersion medium from the slurry of this invention, and forming a composite resin material. And in the manufacturing method of the composite resin material of this invention, since the slurry mentioned above is used, it can obtain the composite resin material which can form the molded object which is excellent in mechanical strength and has a sufficiently low surface resistivity. it can.
  • the method for removing the dispersion medium from the slurry is not particularly limited, and a known method such as drying or filtration can be used.
  • a method for removing the dispersion medium drying is preferable, vacuum drying, drying by distribution of an inert gas, drying using a spray dryer and drying using a CD dryer are more preferable, and vacuum drying and a spray dryer are used. More preferred are drying using a CD dryer and a CD dryer.
  • a composite of a fluororesin and a fibrous carbon nanostructure obtained by removing a dispersion medium from a slurry may be used as it is as a composite resin material.
  • the composite resin material may be granulated by any method such as pulverization or flaking.
  • the manufacturing method of the molded object of this invention includes the process of shape
  • the molding of the composite resin material is not particularly limited, and can be performed using a known molding method such as compression molding. Moreover, you may give a baking process arbitrarily to the molded object obtained by shape
  • the molded object obtained using the manufacturing method of the molded object of this invention becomes surface resistivity less than 1 * 10 ⁇ 8 > ohm / sq, for example, Preferably it is less than 1 * 10 ⁇ 7 > ohm / sq.
  • the volume fraction of the fibrous carbon nanostructure was determined using a composite resin material (total solid content) obtained by removing the dispersion medium from the slurry. Specifically, the produced composite resin material was subjected to 20 ° C./20° C. in a temperature range of room temperature to 700 ° C. in a nitrogen atmosphere using a thermogravimetric measuring device (manufactured by TA Instruments, product name “Discovery TGA”).
  • the temperature was raised at a rate of minutes, and the resin (fluororesin) was thermally decomposed by holding at 700 ° C. for 5 minutes. Then, the weight (W P ) of the resin in the composite resin material was calculated. Next, switching from the nitrogen atmosphere to the air atmosphere, holding at 700 ° C. for 10 minutes in the air atmosphere, and decomposing the fibrous carbon nanostructure, the weight of the fibrous carbon nanostructure in the composite resin material (W C ) was calculated. Then, from the specific gravity ⁇ P of the resin and the specific gravity ⁇ C of the fibrous carbon nanostructure, the volume fraction (V) of the fibrous carbon nanostructure in the solid content contained in the slurry using the following formula: Asked.
  • the obtained test piece was measured for tensile strength and tensile elongation at 23 ° C. in accordance with JIS K7137-1. Higher tensile strength and tensile elongation at 23 ° C. indicate better mechanical properties.
  • a molded body molded using a composite resin material containing fibrous carbon nanostructures has a lower tensile strength than a molded body molded using a resin material not containing fibrous carbon nanostructures.
  • the ratio of the tensile strength (the tensile strength of the molded body molded using the composite resin material containing the fibrous carbon nanostructure / the molding molded using the resin material not containing the fibrous carbon nanostructure.
  • the tensile strength of the body is preferably 0.80 or more, more preferably 0.85 or more, and further preferably 0.90 or more.
  • tensile elongation may be lowered by adding a fibrous carbon nanostructure.
  • the ratio of the tensile elongation (the tensile elongation of the molded body formed using the composite resin material containing the fibrous carbon nanostructure / the molding formed using the resin material not containing the fibrous carbon nanostructure.
  • the tensile elongation of the body is preferably 0.80 or more.
  • the area ratio S of the aggregate of a fibrous carbon nanostructure was measured.
  • the results are shown in Table 1.
  • the slurry was centrifuged using a centrifuge (product name “Spinning & Revolving Mixer Awatori Nertaro ARE-310”, manufactured by Shinky Corporation), and then the supernatant dispersion medium was removed.
  • the composite (composite resin material) which combined the fluororesin and the carbon nanotube was obtained by vacuum-drying at 80 degreeC for 12 hours with a vacuum dryer (made by Yamato Kagaku company).
  • the volume fraction V of the fibrous carbon nanostructure was calculated
  • the obtained composite was pulverized with a mill mixer, and the composite resin material particles were put into a mold. Then, using a compression molding machine (manufactured by Dumbbell, model number “SDOP-1032IV-2HC-AT”), 20 Preliminary molding was performed under the conditions of ° C., pressure of 21 MPa, and pressure holding time of 5 minutes to obtain a sheet-shaped preform having a length of 130 mm ⁇ width of 80 mm and a thickness of 20 mm. After the preform was removed from the mold, it was fired at 370 ° C. for 6 hours in a hot air circulating furnace in a free state to obtain a molded body. And about each of the obtained molded object, each evaluation of surface resistivity, tensile strength, and elongation was performed. The results are shown in Table 1.
  • Example 2 When preparing the slurry, a slurry, a composite resin material and a molded body were prepared in the same manner as in Example 1 except that the rotation speed of the homogenizer was changed to 15000 rpm and the stirring time was changed to 30 minutes. And evaluated. The results are shown in Table 1.
  • Example 5 When preparing the slurry, a slurry, a composite resin material and a molded body were prepared in the same manner as in Example 1 except that the amount of carbon nanotubes was changed to 0.05 g, and evaluation was performed in the same manner as in Example 1. It was. The results are shown in Table 1.
  • Example 6 When preparing the slurry, a slurry, a composite resin material and a molded body were produced in the same manner as in Example 1 except that the amount of carbon nanotubes was changed to 0.2 g, and evaluated in the same manner as in Example 1. It was. The results are shown in Table 1.
  • Example 2 When preparing slurry, a slurry was obtained by carrying out dispersion treatment at a pressure of 100 MPa using a wet jet mill (product name “L-ES007”, manufactured by Yoshida Kikai Kogyo Co., Ltd.) instead of the homogenizer. In the same manner as in Example 1, a slurry, a composite resin material, and a molded body were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 1 Using only the fluororesin particles used in Example 1 (manufactured by Daikin Industries, PTFE (polytetrafluoroethylene) molding powder, product name “Polyflon PTFE-M12”, average particle size: 50 ⁇ m, specific gravity: 2.16)) A molded body was produced in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • PTFE polytetrafluoroethylene
  • the composite resin material which is excellent in mechanical strength and can form the molded object with sufficiently low surface resistivity can be obtained.
  • a composite resin material that is excellent in mechanical strength and capable of forming a molded article having a sufficiently low surface resistivity can be obtained.
  • a molded article having excellent mechanical strength and sufficiently low surface resistivity can be obtained.

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Abstract

L'invention a pour objet de fournir un matériau de résine composite qui permet de former un corps moulé d'une excellente résistance mécanique, et de résistivité superficielle suffisamment basse. Le procédé de fabrication de matériau de résine composite de l'invention inclut une étape au cours de laquelle est retiré un milieu de dispersion d'une bouillie. Laquelle bouillie comprend des particules de résine fluorée, une nanostructure de carbone sous forme de fibres et le milieu de dispersion, et contient la nanostructure de carbone sous forme de fibres selon une proportion supérieure ou égale à 0,01 partie en masse et inférieure ou égale à 0,5 partie en masse pour 100 parties en masse de particules de résine fluorée. Lorsque la bouillie est introduite dans une lame de verre rainurée de 0,5mm de profondeur, et qu'une plage de ３ｍｍ×２ｍｍ à l'intérieur d'une rainure de la lame de verre est observée à l'aide d'un microscope optique, le rapport surfacique (S) (en %) d'un agrégat de la nanostructure de carbone sous forme de fibres, et le rapport volumique (V) (en %) de la nanostructure de carbone sous forme de fibres dans la matière solide de la bouillie, satisfont la formule relationnelle : ３≦Ｓ／Ｖ≦３０.
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WO2023162899A1 (fr) * 2022-02-28 2023-08-31 日本ゼオン株式会社 Procédé de production de particules de résine composite, composition antistatique et objet moulé
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